Olefin hydrogenation over synthetic amorphous silica

ABSTRACT

Hydrogenation-dehydrogenation of suitable feedstock is provided wherein such feedstock is subjected to hydrogenation-dehydrogenation conditions in the presence of a catalytic amount of a solid containing, at least in part, a synthetic amorphous solid prepared by hydrolyzing and polymerizing in the presence of water a silane having the formula R(Si)X 3 , wherein R is a nonhydrolyzable organic group, X is a hydrolyzable group and (Si) is selected from the group consisting of ##STR1## and calcining the polymerized product, said silane being admixed with a second component, R&#39; n  MY m , wherein R&#39; is selected from the group consisting of the same groups as R, Y is selected from the group consisting of the same groups as X and oxygen, M is at least one member selected from the group consisting of the elements of Groups IIIA, IVA, VA, IVB, VB, VIB, VIIB and VIII of the Periodic Table, m is any number greater than 0 and up to 8 and n is from 0 to any number less than 8.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a division of application Ser. No. 876,813, filed Feb. 10, 1978,now U.S. Pat. No. 4,174,356, which was a continuation-in-part ofapplication Ser. No. 738,789, filed Nov. 4, 1976, now U.S. Pat. No.4,086,261, which was a continuation-in-part of application Ser. No.638,405, filed Dec. 8, 1975, now U.S. Pat. No. 4,003,825, which was adivision of application Ser. No. 450,967, filed Mar. 14, 1974, now U.S.Pat. No. 3,983,055.

BACKGROUND OF THE INVENTION

(1) Field of the Invention

This invention relates to use of specifically prepared amorphoussynthetic siliceous materials, as catalysts inhydrogenation-dehydrogenation of suitable chemical feedstock. Suchfeedstock for hydrogenation may be any unsaturated hydrocarbons of from2 to about 30 carbon atoms, e.g. isobutene; or organic compoundscontaining carbonyl groups and having from 1 to about 30 carbon atoms,e.g. aldehydes and ketones. Such feedstock for dehydrogenation may beany saturated or partially unsaturated hydrocarbons, especiallyparaffins of from 2 to about 30 carbon atoms, olefins of from 2 to about30 carbon atoms or naphthenes of from 5 to about 30 carbon atoms; oralcohols of from 1 to about 30 carbon atoms.

(2) Description of the Prior Art

U.S. Pat. No. 2,441,214 discloses a hydrocarbon conversion catalystprepared by reacting an aluminum, magnesium or zirconium compound, suchas AlCl₃, with dehydration product of a silanol or siloxane polymer R₃SiOSiR₃, ##STR2## R being alkyl, aryl or aralkyl, to produce a metalcomplex, precipitating in water plus base (NH₄ OH), water-washing anddrying. In one example, the product was calcined for 3 hours at 500° C.This procedure is not the same as that utilized in the presentinvention, and it results in loss of silicon values with lower surfacearea and fewer small pores than desirable.

U.S. Pat. No. 2,483,963 discloses the hydrolysis of organochlorosilanesto produce organosiloxanes. The process involves introducing liquidsilane into the upper end of a silane-water vapor contact zone andremoving a condensed siloxane. The amount of water used is in excess ofthat necessary to hydrolyze the silane. The trichloro, RSiCl₃, in whichR is alkyl or aryl, is either not used at all or used in a restrictedamount so that in the formula RnSiCl_(4-n), n is at least 1.7.

In U.S. Pat. No. 2,722,504 is disclosed a catalyst material havingcomponents of an activated silica or alumina, an oxide or sulfide ofcertain transition metals and an organophilic silicone coating formed by(1) adsorbing onto the activated surface of the first component a silanemonomer of the formula ##STR3## wherein X is a hydrolyzable group, R₁ isnon-hydrolyzable and R₂ and R₃ may each be hydrolyzable or not, (2)hydrolyzing the monomer, then (3) heating the combined materials at 800°F. to 1200° F. to dry; the second metal component is added byimpregnation, or alternatively is added with the silane monomer.

In U.S. Pat. No. 3,661,770 there is disclosed a method of preparing acatalyst by using a chlorosilane compound, SiX₄, at least one of the X'sbeing chlorine and the others hydrogen, methyl, ethyl, methoxy andethoxy with a Group VIII metal-alumina composite at a temperature of500° F. to 900° F. The composite is the catalyst and the silane is anactivating agent.

SUMMARY OF THE INVENTION

It has now been discovered that shape-selectivity or the pore-sizedistribution of a silica or silica-containing composition may becontrolled by the steps of (1) hydrolyzing a mono-organo silane,R(Si)X₃, alone or in the presence of other compounds having the formulaR'_(n) MY_(m), wherein the R groups and R' groups are organicnon-hydrolyzable groups and may be the same or different, X is ahydrolyzable group, Y is the same as X or oxygen, and M is either ametal or non-metal of the groups of the Periodic Table including siliconother than Groups IA, IIA, VIIA and O, m is a number up to 8 and n iszero or a number less than 8, or an inorganic ionic compound containingM and Y, (2) bringing about the condensation and polymerization of thehydrolyzed compounds and (3) calcining the polymerized product. It hasfurther been discovered that the calcined silica-containing productsabove have utility in a process for hydrogenation-dehydrogenation ofsuitable organic compound feedstocks, such as, for example hydrogenationof unsaturated hydrocarbon compounds; organic compounds containingcarbonyl groups, including ketones and aldehydes; and dehydrogenation ofsaturated or partially unsaturated hydrocarbon compounds, includingnaphthenes, paraffins and olefins.

In the following discussion, "silica products" or "silica structures"and similar terms are intended to include materials as described herein,containing components other than silica alone. Also as used herein, theterm "hydrolyzable" refers to any group which is capable of conversionto hydroxy in the presence of water under conditions of the hydrolysisstep "non-hydrolyzable" refers to any group which does not convert tohydroxy under the said conditions.

DESCRIPTION OF SPECIFIC EMBODIMENTS

This invention provides a hydrogenation-dehydogenation process utilizingas a catalyst a solid having shape-selectivity for hydrocarbonconversion and other processes but without the cost of many of the knownshape-selective catalysts. The present invention provides inexpensivecatalysts of controlled pore size whose adsorptive characteristics canbe designed to accept within the pores thereof hydrocarbon molecules ofdifferent shapes. Furthermore, this invention provides a silicastructure which may be used alone as a catalyst or as the selectivecarrier for more active components.

Formation of the silica structures for use in this invention is carriedout by the steps of hydrolyzing the silane, polymerizing the hydrolysisproducts and calcining the polymerized product. The silanes used information of the silica structures useful in this invention have theformula R(Si)X₃ wherein R is an organic radical which cannot behydrolyzed in the above hydrolyzing step and X is a hydrolyzable groupwhich ultimately converts the silane to a siloxane polymer. As used inthis invention, R may be alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl,alkaryl, aralkyl, or a heterocyclic group containing oxygen, sulfur ornitrogen in the ring, aminoalkyl (including polyamino alkyl), and thehalo and hydroxy derivatives of such groups, R having preferably from 1to about 40 carbon atoms; the expression (Si) may be a single siliconatom or ##STR4## X may be halogen, hydrogen, alkoxy, aryloxy of from 1to about 20 carbon atoms, alkali metaloxy, carboxy, nitro, amino and thelike. The preferred compounds useful in forming the silica structure foruse in this invention are those in which R is alkyl or aryl or a groupcontaining one or more amino groups and X is halogen or alkoxy.Non-limiting examples of R include methyl, ethyl, butyl, hexyl, decyl,dodecyl, octadecyl, phenyl, tolyl, naphthyl, aminomethyl, aminoethyl,aminopropyl, ethylenediaminomethyl, ethylenediaminopropyl, cyclohexyl,chlorobutyl, hydroxybutyl, ethoxyethyl, propoxypropyl and the like.Non-limiting examples of X include chloro, bromo, iodo, methoxy, ethoxy,acetoxy and the like.

Normally hydrolysis would convert hydrolyzable groups to hydroxy.However, trihydroxy organosilanes would lead instead to organosiloxanepolymers by dehydrocondensation. Molecular weights ranging from 2500 to3,000,000 or more are usually obtained.

Depending on the amount of water present in the hydrolysis reactionmixture and the type of R group, the intermediate polymerization productis either a three-dimensional cage-containing structure or atwo-dimensional linear or sheet-containing structure. Thecage-containing structure is the preferred structure in this inventionfor producing the more desirable silica, although it is likely that thehydrolysis step produces both types of polymer in the same reactionmixture. For this reason, the amount of water used in the hydrolysis ispreferably kept to the stoichiometric amount or slightly in excess ofthat necessary to convert the X groups to hydroxy. It is preferred touse a system of an organic solvent and water instead of water alone.Excess water also has been found to affect the distribution of the poresizes in the finished calcined product. It is preferred to use 0.5:1 to10:1 by volume of organic solvent to water. The preferred solvents arehydrocarbons, e.g. hexane and benzene, ethers and alcohols, thepreferred alcohols being methanol, ethanol and other lower alcohols.However, solubility of the silane in the water-solvent system is notnecessary, providing the water control is maintained throughout thehydrolysis step. Hence, any convenient solvent system is useful.

The silane is added to the solvent-water mixture and stirred. An acid orbase hydrolysis/condensation catalyst may be used. Hydrolysis may beeffected at a temperature as low as room temperature and up to about200° C. Usually a solid precipitate or a thick syrup is produced. Theprecipitated polymer may be separated from the reaction mixture byfiltration. The semi-solid polymer may be separated by boiling off theliquids preferably under vacuum. The remaining structure is understoodto consist of the following repeating group: ##STR5## If the silane ishydrolyzed alone, without a second dissimilar component present, thepolymeric structure is understood to be primarily a cage-typethree-dimensional network molecule. Other silanes may be present in thehydrolysis step. Other tri-X silanes of different R groups or mono-X ordi-X silanes of the same or different R groups will provide a cagemolecule of differing channels or pore characteristics. Generally, the Rgroup determines the size of the pores of the final product, the smallerthe R group the smaller the pore.

The siloxane polymer resulting from the hydrolysis step is thensubjected to stepwise or programmed calcining. Essentially, calciningreplaces the R groups of the polymer with hydroxy, or oxy groupsdepending upon whether pairs of hydroxy groups are formed close enoughto each other to condense or, if calcining is done in the absence ofair, hydrogen. Clearly the gaps caused by the removed R groups form thesmall pores. Calcining is carried out at the minimum elevatedtemperature necessary to remove the R groups, normally from about 200°C. to below the sintering temperature, usually 200° C. to 600° C.,preferably from 350° C. to 550° C., and at rates of increase from 10° C.to 300° C. per hour, preferably 20° C. to 250° C. (or from 0.3° C. toabout 4° C. per minute).

When the calcining step is carried out in air, hydroxy or oxy or even-M-O- groups (if a second component is present) occur in the product. Inthe absence of air, it is believed that ##STR6## groups occur by freeradical mechanism.

Preparation of a small pore size material with a high degree ofcross-linking (three-dimensional structure) may be obtained by usingR(Si)X₃ alone or with other silanes in which R is a low alkyl. Someselectivity for particular hydrocarbon molecules to be sorbed, otherwiseobtainable with R(Si)X₃, may be lost in final products obtained whenSiX₄, R₂ (Si)X₂ or R₃ (Si)X are in the initial reaction mixture. Sincecontrol of shape selectivity is one of the desirable ends of thisinvention, as well as producing stable three-dimensional structures, itis most preferred that the R(Si)X₃ be the only silicon reactant; if amixture of silanes is used, it is preferred that at least about 33% byweight of the silanes be R(Si)X₃. For example, a product derived fromphenyl trichlorosilane has a slightly lower pore volume than that of aproduct obtained from a mixture of 80% phenyl trichlorosilane and 20%diphenyl dichlorosilane, but the selectivity for n-hexane was higher inthe first product.

Surface areas also vary with R, methyl producing a relatively low area,bulkier groups such as cyclohexyl or phenyl producing products of over300 m² /g.

The R(Si)X₃ silane may be hydrolyzed in the presence of R'_(n) MY_(m),in which R' is the same as or different from R, Y is any combininggroup, preferably halogen or alkoxy, aryloxy, metaloxy, hydroxy or oxy,M is a metal or non-metal, preferably of Periodic Groups IIIA, IVA, VA,IVB, VB, VIB, VIIB, and VIII, m is a number up to 8, and n is 0 or anumber less than 8. In addition, inorganic ionic compounds consisting ofan anion of M and Y with a cationic portion may be used. Suitablecations include hydrogen, alkali and alkaline earth metals and ammonium.An M-containing compound may also be a complex having as one ligand asuitable group such as amine or phosphine which latter is part of an Rgroup on silicon. In particular, the amorphous silica solids of thisinvention may have incorporated therewith zirconium, thorium, chromium,iron, molybdenum, rhodium, tungsten, copper, tin, titanium, vanadium,cobalt, nickel, zinc, silver, ruthenium, palladium, platinum, and thelike, and mixtures thereof with each other and/or with aluminum.

The second component is combined with the R(Si)X₃ in a solvent system inthe hydrolysis step. These combination products, as with the silicaproducts alone, are also amorphous solids of varying pore sizes andsurface areas.

The silane is combined with one or more members of the second componentin the presence of water and solvent, again water being in preferablystoichiometric, or only slightly over stoichiometric amounts. Ifnecessary a small quantity of a base acting as a catalyst for promotingthe polymerization of the mixture may be present, such as pyridine,pyrimidine, triethylamine or ammonia. The resulting solid is removed andsubjected to calcination to produce the desired material.

Such compounds as aluminum chloride, aluminum butoxide, aluminumethoxide, aluminum propoxide, sodium aluminate, ethyl aluminum chloride,methyl aluminum chloride, boric acid, sodium borate, methyl borate,cobalt chloride, nickel chloride, nickel acetate, phenyl phosphite orphosphonate, butyl phosphonate, phenyl dichlorophosphine, palladiumchloride, methylamine palladium chloride, palladium nitrate,chloroplatinic acid, potassium chloroplatinate, cyclooctadienyl platinumdichloride, butyl tin acetate, tin chloride, di-cyclopentadienyltitanium chloride, titanium chloride, vanadium chloride, vanadium oxideare suitable as the second component in this invention. Secondcomponents containing Group VIII metals, such as, for example, iron,nickel, cobalt, platinum and/or palladium, are preferred. Particularlypreferred second components are those containing the mixtures of one ormore Group VIII metals with aluminum.

In addition, known methods of exchange or impregnation can be used toincorporate additional metals for the purpose of producing catalysts.

In general, unsaturated hydrocarbon compounds of from 2 to about 30carbon atoms or organic compounds containing one or more carbonyl groupsand having from 1 to about 30 carbon atoms may be catalyticallyhydrogenated in the presence of a catalytically effective amount of theabove-defined specifically prepared amorphous synthetic siliceousmaterial over a range of catalytic hydrogenation conditions, including atemperature of from about 0° C. to about 400° C., preferably from about25° C. to about 250° C., a pressure of from about 1 atmosphere to about25 atmospheres, preferably from about 5 to about 10 atmospheres, ahydrogen/feedstock mole ratio of from about 2 to about 100, preferablyfrom about 18 to about 75, and a liquid hourly space velocity (LHSV) offrom about 0.1 hr.⁻¹ to about 100 hr.⁻¹, preferably from about 0.5 hr.⁻¹to about 75 hr.⁻¹. The hydrogen circulation for this reaction depends,of course, upon the particular feedstock being hydrogenated and may varyfrom about 2000 scf/bbl to about 15,000 scf/bbl, preferably from about7,000 scf/bbl to about 12,000 scf/bbl.

When dehydrogenation is conducted for a feedstock comprising essentiallya saturated or partially unsaturated hydrocarbon, e.g. paraffin of from2 to about 30 carbon atoms, olefin of from 2 to about 30 carbon atoms ornaphthene of from 5 to about 30 carbon atoms, a temperature of fromabout 200° C. to about 750° C., preferably from about 500° C. to about700° C., a pressure of from about 0.1 atmosphere to about 25atmospheres, preferably from about 0.2 to about 3 atmospheres, and aLHSV of from about 0.1 hr.⁻¹ to about 10 hr.⁻¹, preferably from about 1hr.⁻¹ to about 3 hr.⁻¹, must be maintained.

When dehydrogenation is conducted for a feedstock comprising an alcoholof from 2 to about 30 carbon atoms, e.g. ethanol, isopropanol andothers, the temperature must be maintained at from about 200° C. toabout 500° C., preferably from about 250° C. to about 400° C., thepressure must be maintained at from about 0.5 atmosphere at about 2atmospheres, preferably at about 1 atmosphere, and the liquid hourlyspace velocity (LHSV) must be maintained at from about 0.1 hr.⁻¹ toabout 10 hr.⁻¹, preferably from about 0.5 hr.⁻¹ to about 5 hr.⁻¹. Whendehydrogenation is conducted for a feedstock comprising methanol,however, the temperature should be maintained at from about 300° C. toabout 500° C., preferably from about 350° C. to about 400° C. and thepressure and LHSV may be maintained as for dehydrogenation of alcoholfeedstock of from 2 to about 30 carbon atoms.

The following examples represent illustrations of the present inventionand are not meant to be limitations thereof. Unless otherwise expressed,amounts and percentages are on a weight basis. Percent yields of thefinal calcined products are based on the weight of the polymer producedafter hydrolysis and polymerization.

EXAMPLE 1

In a suitable vessel was added 25 ml of phenyl trichlorosilane to asolution of 15 ml of water and 60 ml of methanol (1:4 v/v). The heatgenerated by this addition brought the mixture to boiling and a whitesolid formed. The mixture was maintained at room temperature for fourdays, after which the solid was removed and washed in ethanol and airdried. The washed solid was calcined in air by heating at 100° C. perhour to 500° C. and held at that temperature for 10 hours.

The resulting product was amorphous by X-ray examination and had thefollowing characteristics:

    ______________________________________                                        Surface Area:         511    m.sup.2 /gm                                      Mean Pore Diameter:   26     A                                                Pore Volume:          0.341  ml/gm                                            Particle Density:     1.28   g/ml                                             Real Density:         2.32   g/ml                                             ______________________________________                                    

    ______________________________________                                        Pore Size Distribution                                                        ______________________________________                                                less than 7 A                                                                               61.0%                                                            7-10        8.0                                                              10-15        3.4                                                              15-25        1.4                                                              25-300       2.1                                                              over 300     24.1                                                     ______________________________________                                    

EXAMPLE 2

In a suitable reactor, 50.4 grams of H₂ NCH₂ CH₂ NHCH₂ CH₂ CH₂ Si(OCH₃)₃was added to 150 ml of the 4/1 v/v methanol-water mixture of Example 1.The mixture was stirred for one hour and allowed to stand for one day.The mixture was then refluxed for 2 hours and the solvent removed undervacuum. The resulting product was calcined at 3° C. per minute to 538°C. and held for 10 hours and then cooled. The yield was 35% by weightbased on the weight of polymer. The product had a surface area of 642 m²/gram.

EXAMPLE 3

In a suitable reactor, 50 grams of BrCh₂ CH(Br)--SiCl₃ was added to 150ml of the 4:1 v/v methanol-water solvent. The mixture was allowed tostand for 2 days. It was refluxed for 2 hours and filtered. The solidswere washed with three 200-ml portions of ethanol and dried in a vacuumoven at 125° C. for 2 hours. The product was calcined by heating at 1°C. per minute to 538° C., and held at that temperature for 10 hours, andfinally cooled. The yield was 27% by weight and the product had a porevolume of 0.15 ml/g, surface area of 242 m² /mg and a particle densityof 1.66 g/ml.

EXAMPLE 4

In a suitable reactor, 50.5 grams of dodecyltrichlorosilane C₁₂ H₂₅SiCl₃ was added to 150 ml of the methanol-water 4/1 v/v solvent and themixture was allowed to stand for 4 days. The mixture was then refluxedat about 60° C. for 2 hours. The product polymer was a viscous liquid.The solvent was decanted and polymer washed three times with 200-mlethanol portions with decanting of the wash each time. The washedproduct was dried in a vacuum oven at 120° C. for 2 hours, calcined at1° C. per minute to 538° C., held at that temperature for 10 hours andcooled. The yield was 20% by weight of a product having the followingcharacteristics: pore volume 0.233 ml/g, surface area 178 m² /g andparticle density 1.59 g/ml.

EXAMPLE 5

A mixture of 55 grams of triphenylhydroxy silane, (C₆ H₅)₃ SiOH, 8 gramsof sodium and 300 ml of benzene was refluxed at 80° C. for 3 hours andallowed to stand without heat for 5 days. The mixture was cooled toabout 10° C. in an ice bath and stirred, and 40 grams of SiCl₄ in 200 mlbenzene was added. The resulting mixture was subjected to reflux at 80°C. for 2 hours and cooled. During the SiCl₄ addition and refluxing, astream of helium was passed through the reactor to exclude moisture. Thereaction mixture was filtered to remove solid by-product. The benzenewas then removed on a ratary evaporator to leave 39.7 grams of theproduct (C₆ H₅)₃ --Si--O--SiCl₃.

In a suitable reactor, 29.6 grams of the above product was added to 150ml of the same methanol-water solvent and the mixture was allowed tostand one day. The mixture was then refluxed at 60° C. for 2 hours andcooled and allowed to stand for 7 days. The viscous white liquid wasseparated from the supernatant solvent, washed three times with 200-mlportions of ethanol. After the first wash, the product was a granularsolid. The washed product was dried in a vacuum oven at 120° C. for 2hours and calcined at 1° C. per minute to 538° C., being held at thattemperature for 10 hours. The yield was 23% by weight; pore volume 0.21ml/g, surface area 341 m² /g, particle density 1.59 g/ml.

EXAMPLE 6

In a suitable reactor, 25 grams of phenyl trichlorosilane and 25 gramsof methyl trichlorosilane were added to 150 ml of the 4/1 methanol-watersolvent. The mixture was allowed to stand for 2 hours and then refluxedfor 2 hours. The solvent was decanted and the white solid washed threetimes with 100-ml portions of water, three times with 100-ml portions ofacetone and three times with 100-ml portions of hexane. The product wasdried in a vacuum oven at 118° C. for 1.5 hours then calcined as inExample 5. The yield was 62% by weight; surface area 355 m² /g.

EXAMPLE 7

A silica compound prepared as in Example 2 was produced by adding to 150ml of a 4/1 v/v mixture of methanol and water 10 grams of SiCl₄, 4 gramsof methyl trichlorosilane, 33.5 grams of dimethyl dichlorosilane and 2grams of trimethyl chlorosilane. The calcination yielded 66% by weightof final product. This product had a pore volume of 0.79 ml/g, a surfacearea of 94 m² /g and a particle density of 0.8 g/ml.

EXAMPLE 8

In a suitable reactor 42 grams of phenyl trichlorosilane and 10.3 gramsof diphenyl dichlorosilane were added to 150 ml of the 4/1 by volumemethanol-water solvent. The mixture was allowed to stand for 6 days. Thesolvent was decanted and the product was washed three times with 300-mlportions of ethanol. The product was dried in a vacuum oven for 16 hoursand calcined as in Example 5. The yield was 27% by weight.

EXAMPLE 9

In a suitable reactor, 100 ml of ethyl trichlorosilane was added to 300ml of the same methanol-water solvent mixture of the previous examples.The mixture was allowed to stand for 10 days, then heated to reflux forone-half hour and again allowed to stand for 2 days. The solvent wasboiled off over a 2-hour period and the product was washed three timeswith 100-ml portions of ethanol and three times with 100-ml portions ofpetroleum ether. The product was air-dried, calcined at 9° C. per minuteto 538° C. held at that temperature for 10 hours and then cooled. Theyield was 73% by weight; pore volume 0.22 ml/g, surface area 90 m² /gand particle density 1.44 g/ml.

EXAMPLE 10

In a suitable reactor 50 grams of methyl trichlorosilane was mixed with150 ml of the 4/1 v/v methanol-water solvent. The mixture was allowed tostand for 7 days. The solvent was decanted and the product washed threetimes with 100-ml portions of ethanol. The product was dried in a vacuumoven at 120° C. for one hour and calcined as in Example 5. The yield was85%, pore volume 0.16 ml/g, surface area 28 m² /g and particle density1.62 g/ml.

A number of silica products were tested for sorption capacity in thefollowing manner. A sample solid of known weight is placed in a quartzbasket suspended from a microbalance (Cahn Instrument Co.) on a quartzrod, all enclosed in a jacketed heater. A carrier gas, helium, is passedthrough a wick saturator to entrain water or hydrocarbon vapor and theninto the microbalance and basket at 100 ml/min. Temperature and weightmeasurements of the solid are continuously made. The temperature ismaintained at 35° C. in the heater. The sorption capacities are reportedat partial pressures in the carrier stream of 20 mm. Hg forhydrocarbons, 12 mm. for water. The following are results for sorptionof n-hexane, 2,3-dimethylbutane, water, cyclohexane, benzene andtriethylamine. For comparison purposes, an aluminosilicate zeolitecatalyst of the ZSM-5 type, described in U.S. Pat. No. 3,702,886, inwhich the cations are predominantly hydrogen (herein referred tp as"HZSM-5"), was also measured for sorption capacity.

    ______________________________________                                        Example                                                                              nC.sub.6                                                                              2,3-DMB  H.sub.2 O                                                                            CycC.sub.6                                                                          C.sub.6 H.sub.6                                                                     TEA                                ______________________________________                                        1      0.17    0.13     0.15   0.13  0.17  0.05                               2      0.32    0.27     0.27   --    --    --                                 3      0.13    0.06     0.10   --    --    --                                 4      0.09    0.02     0.10   0.04  0.09  --                                 8      0.10    0.11     0.16   --    --    --                                 9      0.09    0.01     0.12   0.06  0.07  --                                 10     0.008   0.006    0.005  --    --    --                                 HZSM-5 0.19    0.16     0.09   --    --    0.12                               ______________________________________                                    

EXAMPLE 11

To a solution of 50 grams of phenyl trimethoxysilane, C₆ H₅ Si(OCH₃)₃,and 10 ml of pyridine in 150 ml of 4:1 methanol-water v/v mixture wereadded 5 grams of aluminum t-butoxide, Al(O-t-C₄ H₉)₃. The mixture wasallowed to stand overnight and was then heated to reflux at about 60° C.for 6 hours. Upon cooling the mixture, a solid precipitated. The solidwas filtered out, washed with ethanol, dried in a vacuum oven and heatedto 538° C. at 1° C./minute in an air stream. It was then cooled yielding11.3 grams of a brown-gray aluminum-silicon solid.

EXAMPLE 12

In a suitable reactor 31.3 grams of ethyl trichlorosilane, CH₃ CH₂SiCl₃, 150 ml of the 4:1 methanol-water mixture and 3 grams of1,5-cyclooctadienyl platinum dichloride were combined. Heat evolved andthe mixture became opaque. After standing overnight, the light yellowsolid and clear liquid so resulting were refluxed at about 60° C. for 16hours and cooled. The solid was filtered out, washed and dried andcalcined as in Example 11, leaving 8.8 grams of a black granularplatinum-silicon product.

EXAMPLE 13

To a vessel containing 750 ml of water was added 82.9 grams of methyltrichlorosilane, the temperature rising to 56° C. The mixture wasstirred for 10 minutes and a white solid precipitate was filtered out,water washed and added to a solution of 20.2 grams of NaOH (equimolar tosilicon) in 63 grams of water. The resulting mixture was stirred for 2hours at 100° C., then 168 grams of methanol was added. Minor solidmatter was removed by filtration, leaving as filtrate an aqueoussolution of CH₃ Si(OH)₂ ONA. To this solution were added 24 grams ofnickel chloride hexahydrate and 13.3 grams of aluminum chloride(equimolar amounts) dissolved in 150 ml of the 4:1 alcohol:watermixture. A light green solid precipitated; an additional 150 ml ofsolvent mixture was added and the system was heated to reflux at about70° C. for 2 hours. The solid product was separated from the supernatantliquid after standing for 16 hours at room temperature. Sodium chloridewas removed with boiling water and methanol, and the washed solid wasdried in vacuum at 120° C. The product was calcined as in Example 11,providing a yield of 38.6 grams of a light tan nickel-aluminum-siliconsolid.

EXAMPLE 14

To a vessel containing 200 ml of absolute ethanol were added 0.839 gramsof PdCl₂ and 51.6 grams of aminoethylaminopropyl trimethoxysilane (theH₂ NCH₂ CH₂ NHCH₂ CH₂ CH₂ Si(OCH₃)₃ of Example 2). After standingovernight the mixture was filtered to remove solid PdCl₂ particles and50 ml of water was added producing a light yellow solution. Noprecipitate formed after 5 days of standing; the solvent was removedunder vacuum, below 33° C., leaving a light yellow solid. The solid wascalcined as in the previous examples; 14.3 grams of a red-brownpalladium-silicon solid was produced containing about 3% palladium.

EXAMPLE 15

In a suitable reactor, 10 grams of aluminum triisopropoxide and 50.6grams of H₂ NCH₂ CH₂ NHCH₂ CH₂ CH₂ Si(OCH₃)₃ were added to 150 ml of the4/1 methanol-water solvent and allowed to stand one day. The mixture wasrefluxed at 60° C. for 2 hours and allowed to stand one more day. It wasagain refluxed for 96 hours. A liter of methanol was added and themixture was heated to boiling, then filtered while hot. The solvent wasremoved from the filtrate with a rotary evaporator, dried in a vacuumoven at 120° C. for 4 hours, then calcined as in Example 11. The yieldwas 51.2%.

EXAMPLE 16

In a suitable reactor 50.9 grams of H₂ NCH₂ CH₂ NHCH₂ CH₂ CH₂ Si(OCH₃)₃,3.35 grams of aluminum tri-ethoxide and 10 ml of pyridine were mixedwith 50 ml H₂ O and 200 ml of methanol and the mixture was heated toreflux for 16 hours. The solvent was stripped under vacuum and theproduct was calcined at 3° C. per minute at 538° C., held at thattemperature for 10 hours and cooled. The yield was approximately 47%.

EXAMPLE 17

In a suitable reactor, 50 grams of phenyl trichlorosilane and 15 gramsof boric acid were added to 150 ml of tetrahydrofuran. The mixture wasstirred for 2 hours, refluxed for 2 hours and allowed to stand for 48hours. The solvent was stripped off with the rotary evaporator underhouse vacuum at 100° C. The product was calcined as in Example 16, butat a rate of 2° C. per minute. The yield was 34%.

EXAMPLE 18

In a suitable reactor, 10 ml of phenyl trimethoxysilane, C₆ H₅Si(OCH₃)₃, 5 grams of vanadium oxy acetylacetonate, 200 ml methanol, 25ml of water and 5 ml of triethylamine were mixed together and allowed tostand for 10 days. The resulting product was filtered out and washedthree times with 100-ml portions of methanol, dried in a vacuum oven at120° C. for 2 hours. The washed product was calcined at 1° C. per minuteto 538° C., held at that temperature for 10 hours. The yield ofvanadium-silicon product was about 50.4% by weight.

EXAMPLE 19

In a suitable reactor, 10 ml of methyl trichlorosilane, 5 ml of dibutyltin diacetate, 200 ml of methanol and 25 ml of water were mixed andallowed to stand for 10 days. The product was treated as in Example 18.The yield of tin-silicon product was about 67% by weight.

EXAMPLE 20

In a suitable reactor were mixed 33 grams of phenyl trichlorosilane and40 grams of phenyl phosphonic acid in 30 ml of methanol and the mixturewas refluxed for 16 hours. The solvent was removed under vacuum on arotary evaporator. The product was an amber viscous material; it wasdissolved in 100 ml of boiling acetone. The acetone was removed byevaporation leaving solid product. Calcining at 3° C. per minute to 538°C., holding for 10 hours at that temperature left a 33.8% yield ofphosphorus-silicon product.

EXAMPLE 21

In a suitable reactor were mixed 94.1 grams of phenyl trichlorosilane,3.34 ml of a solution of 0.113 gram/ml of sodium ethylene,chloroplatinate in ethanol and 15.8 grams of phenyl dichlorophosphine.Slowly added dropwise to the mixture was 200 ml of 1/1 by volumemethanol-water mixture. Foaming and a heavy white precipitate resulted.The product was filtered out, washed with about 2000 ml of methanol andcalcined as in Example 18. A 25% yield of phosphorus-platinum-siliconproduct was obtained.

EXAMPLE 22

A solution of CH₃ Si(OH)₂ ONa, prepared as in Example 13, was mixed with24.1 grams of CoCl₂.6H₂ O and 13.3 grams of aluminum chloride dissolvedin 150 ml of the 4/1 v/v methanol-water solvent. Another 150-ml solventportion was added, the mixture was refluxed for 2 hours and then cooled.Solids were filtered out, and 1000 ml of boiling water was passedthrough the filter paper to remove NaCl. The solids were washed threetimes with 500-ml portions of methanol, dried in a vacuum oven at 120°C. for 16 hours and calcined at 3° C. per minute to 500° C., being heldat that temperature for 10 hours, and finally cooled. The yield ofcobalt-aluminum-silicon product was 84.4%. The physical characteristicsof the products of Examples 11 to 22 are as follows:

    ______________________________________                                        Product             Pore     Surface Particle                                 of      Percent     Volume,  Area,   Density,                                 Example of M        ml/g     m.sup.2 /g                                                                            g/ml                                     ______________________________________                                        11      6.3    (Al)     0.284  334     1.52                                   12      3.19   (Pt)     0.086  117     1.94                                   13      13.2   (Ni)                                                                   6.8    (Al)     1.43   240     0.56                                   14      3.0    (Pd)     0.512  832     1.06                                   15      9.7    (Al)     --      52     --                                     16      1.1    (Al)     --     296     --                                     17      7.72   (B)      --     below 5 --                                     18      0.22   (V)      --     --      --                                     19      0.1    to                                                                     1.0    (Sn)     --     --      --                                     20      24.0   (P)      1.345   35     0.542                                  21      0.5    (P)                                                                    0.02   (Pt)     --     354     --                                     22      15.2   (Co)     1.030  191     0.740                                  ______________________________________                                    

EXAMPLE 23

The product catalyst of Example 14 was used in this process in whichisobutene was hydrogenated. The sample of solid catalyst used contained3% Pd and had a surface area of 799 m² /gm and a pore volume of 0.512ml/gm. The procedure of the reaction was as follows: A 100 mg (0.25 ml)sample was placed in a vertical glass tube and treated with H₂ at 138°C. and atmospheric pressure. A second stream of isobutene was added and,after 0.5 minute, a sample of the product stream was analyzed by gaschromatography.

At a temperature of 138° C. with a feed of hydrogen and isobutene in amole ratio of 75:1, at a LHSV of 72 and one atmosphere pressure,conversion of 94.8% was obtained.

EXAMPLE 24

In this example, a quantity of isopropanol is dehydrogenated by beingpassed over a fixed bed of 12 mg of a catalyst prepared as in Example 13at 350° C., one atmosphere pressure and a LHSV of 1 hr⁻¹. Thedehydrogenation product obtained is acetone.

EXAMPLE 25

A 100 mg sample of the product catalyst of Example 18 containing 0.22%vanadium is contacted at 550° C. and atmospheric pressure with a streamof n-butane at a LHSV of 1 hr⁻¹. A sample from the product stream after10 minutes is determined by gas chromatography to contain butenes.

EXAMPLE 26

A 100 mg sample of the product catalyst of Example 22 containing 15.2%cobalt is contacted in a vertical glass tube at 600° C. and 3atmospheres pressure with a stream of cyclohexane at a LHSV of 3 hr⁻¹.Analysis of a sample from the product stream taken after one hourindicates the product benzene.

EXAMPLES 27-30

In these experiments, isopropanol is contacted with 100 mg each ofproduct catalyst of Examples 12, 13, 18 and 19 in four separate reactionvessels. In each instance, a reaction product of acetone is observed.The experiment of Example 27 is conducted at 150° C., atmosphericpressure and a LHSV of 2 hr⁻¹. Conditions of Example 28 are 200° C., 2atmospheres and a LHSV of 3 hr⁻¹. Example 29 is conducted at 225° C., 10atmospheres and a LHSV of 4 hr⁻¹. The conditions of Example 30 are 250°C., atmospheric pressure and a LHSV of 5 hr⁻¹.

EXAMPLE 31

The experiment of Example 23 is repeated using 100 mg of the productcatalyst of Example 13, a temperature of 200° C., a pressure of 3atmospheres, a feedstock of diisobutylene and 4 moles of hydrogen/moleof diisobutylene to obtain product of cyclohexane.

As indicated previously, the silica structures of this invention may becontrolled to have shape selectivity toward certain hydrocarbonmolecules. One desirable small pore size distribution will accept normalmolecules and exclude branched isomers. The incorporated components withthe silica do not effect this shape selectivity adversely. Pore sizedistributions (in percent) are as follows:

    ______________________________________                                        Pore                                                                          Radius, A  Ex. 11     Ex. 12     Ex. 14                                       ______________________________________                                        below 7    35.7%      24.6       0.0                                           7-10      8.4        18.9       50.8                                         10-15      1.6        26.4       27.2                                         15-25      0.3        2.4        2.3                                          25-50      0.0        3.3        0.3                                          50-75      0.0        2.9        0.4                                           75-100    0.0        2.4        0.2                                          100-200    0.0        4.0        0.3                                          200-300    0.0        1.1        0.2                                          over 300   54.0       14.0       18.3                                         Total Vol. 0.284      0.086      0.512                                        Vol. below                                                                    15 A       0.130      0.060      0.399                                        ______________________________________                                    

We claim:
 1. A hydrogenation process wherein an olefin of from 2 toabout 30 carbon atoms is subjected to hydrogenation conditions includinga temperature of from about 0° C. to about 400° C., a pressure of fromabout 1 atmosphere to about 25 atmospheres, a hydrogen/feedstock moleratio of from about 2 to about 100, and a liquid hour space velocity(LHSV) of from about 0.1 hr.⁻¹ to about 100 hr.⁻¹, contacting acatalytic amount of a solid containing, at least in part, a syntheticamorphous solid prepared by the steps of hydrolyzing and polymerizing inthe presence of water a silane having the formula R(Si)X₃, wherein R isa non-hydrolyzable organic group, X is a hydrolyzable group and (Si) isselected from the group consisting of ##STR7## and calcining thepolymerized product, said silane being admixed with a second compound,R'_(n) MY_(m), wherein R' is selected from the group consisting of thesame groups as R, Y is selected from the group consisting of the samegroups as X and oxygen, M is at least one member selected from the groupconsisting of the elements of Groups IIIA, IVA, VA, IVB, VB, VIB andVIII of the Periodic Table, m is any number greater than 0 and up to 8and n is from 0 to any number less than
 8. 2. The process of claim 1wherein R of said catalyst material is a member selected from the groupconsisting of alkyl, cycloalkyl, aryl, alkenyl, cycloalkenyl and saidmembers hydroxy-substituted, halogen-substituted and amino-substituted.3. The process of claim 1 wherein X of said catalyst material is amember selected from the group consisting of halogen and alkoxy of from1 to 10 carbon atoms, alkali metaloxy, alkaline earth metaloxy, carboxyand amino.
 4. The process of claim 3 wherein X is chlorine.
 5. Theprocess of claim 3 wherein X is alkoxy.
 6. The process of claim 5wherein X is methoxy.
 7. The process of claim 4 wherein R(Si)X₃ isselected from the group consisting of phenyl trichlorosilane, (C₆ H₅)₃Si--O--SiCl₃, methyl trichlorosilane, ethyl trichlorosilane, dodecyltrichlorosilane and mixtures thereof.
 8. The process of claim 1 whereinthe calcination step in preparation of said catalyst material is carriedout at a temperature of from about 200° C. to about 600° C.
 9. Theprocess of claim 1 wherein M of said catalyst material is a memberselected from the group consisting of molybdenum, silver, nickel,zirconium, tungsten, chromium, copper, manganese, zinc, cobalt,vanadium, titanium, platinum, palladium, iron, boron and mixturesthereof with each other and/or with aluminum.
 10. The process of claim 9wherein M is the mixture of vanadium and molybdenum.
 11. The process ofclaim 9 wherein M includes aluminum as an aluminum alkoxide of from 1 to10 carbon atoms.
 12. The process of claim 9 wherein M includes aluminumas aluminum chloride.
 13. The process of claim 1 wherein M of saidcatalyst material is a member of Group VIII of the Periodic Table ofElements.
 14. The process of claim 13 wherein there is present in thefinal calcined catalyst material a member selected from the groupconsisting of platinum and palladium.
 15. The process of claim 9 whereinthere is present in the final calcined catalyst material aluminum and amember selected from the group consisting of cobalt and nickel.
 16. Theprocess of claim 9 wherein there is present in the hydrolysis andpolymerization steps in preparation of said catalyst material aninorganic compound consisting of an anion of M and Y and a cationselected from the group consisting of hydrogen, alkali metal, alkalineearth metal and ammonium.
 17. The process of claim 16 wherein saidinorganic compound is selected from the group consisting of boric acid,sodium ethylene chloroplatinate, chloroplatinic acid and sodiumaluminate.
 18. The process of claim 1 wherein the steps of hydrolyzingand polymerizing in preparation of said catalyst material are carriedout in the presence of water and an organic solvent.
 19. The process ofclaim 18 wherein the organic solvent is an alcohol.
 20. The process ofclaim 19 wherein the alcohol is methanol.
 21. The process of claim 1wherein the steps of hydrolyzing and polymerizing in preparation of saidcatalyst material are carried out in the presence of water and a base.22. The process of claim 21 wherein the base is selected from the groupconsisting of pyridine and triethylamine.